Method of producing integral waterproofing emulsions and products thereof



p Patented Feb. 25, v

.- UNlTED ,sTATEs PATENT OFFlCE- IHE'IHOD OF PRODUCING INTEGRAL WATERPROOFING EMULSIONS AND PRODUCTS THEREOF Charles H Schuh, Brooklyn, N. Y., assignor to Bakelite Building Products 00., Inc, New York, N. Y., a corporation of Delaware No Drawing. Application April 9, 1938,

Serial No. 201,082

16 Claims.

The present invention relates to waterproofing emulsions and to methods of producing highly efiective integral waterproofing emulsions.

As those skilled in the artknow, the water absorption of various products may ber'educed by the addition of suitable water-repellent materials which are distributed throughout the body of such products. Thus, rosin was-extensively usedin the preparation of paper, as were other resins and waxes; .Calcium soaps were used to a great extent in attempted waterproofing Y of cement and concrete. Asphalts were used in felt and paper bases for roofing, in concrete and for the purpose of road building.

These conventional water-repellent agents were generally mixed as uniformly as possible with the composition during the manufacture of the various products. Clearly, it was diflicult or even impossible to obtain uniform distribution of these water-repellent agents in' an aqueous medium. More recently, these agents werefre'quentlyused in the form of emulsions which made it possible to obtain a much better distribution with a greater ease. The trend of development was to employ finer and finer suspensions of the agent in the emulsion and consequently also in the finished product in which the emulsion was incorporated. More particularly, those skilled in the art were firmly convinced that emulsions of water-repellent agents which are to be incorporated into various compounds, should be very finely dispersed and well stabilized to preserve theagent in concrete and similarproducts, it is 45 clearly stated that in order to be satisfactory for the purpose contemplated, the emulsion must be miscible with-water in all proportions without breaking down. other words, the emulsion had to be finely dispersed and well stabilized.

0 Although these priorwaterproofing emulsions were satisfactory to a certain limited extent for various specific uses, their usefulness has been a frequently questioned by the experts and was held to be highly problematic even in the case of;

ordinary cement andeoncrete products .which normally have about 10% to 1 of v I h ve found them to be altogether unsuitable where the product has any degree of porosity and a substantial degree of water imperviousness. is

desired. Thus conventional emulsions completely failed as integral waterproofing agents in cellular compositions having a substantial percentage of voids, for example, they failed with the cement-fiber products of my copending application Serial No. 60,447, filed January 23, 1936,

tributed voids. The high percentage of voids probably explains why the effectiveness of conventional waterproofing agents in such products is practically insignificant even where such agents are employed in substantial quantities.

Although various suggestions and proposals were made to solve the outstanding problem, none, as far as I am aware, was completely satisfactory and successful on a practical and industrial scale. I

V I have discovered. that the problem may be solved in a remarkably simple manner.

It is an object of the present invention to provide a method for producing a highly effective integral waterproofing emulsion of novel and irnproved character which is free from the disadvantages of prior waterproofing emulsions.

It is. an object of my invention to form as by high speed mixing, an oil-in-water emulsion comprising water-repellent ,materials, solid or semi-solid at normal atmospheric temperature and a weak dispersing agent, preferably soap,.

the individual particlesof which emulsion are normally characterized by non-adherent properties, but which upon dilution are-transformed to particle groups exhibiting adherent qualities and without reversing the emulsion.

It is another object of my. invention to provide an aqueous emulsion of water-repellent material that is stable in normal handling but that undergoes a transformation upon aqueous dilu-' tion without the aid of a strong electrolyte.

A further object of my invention is the prepa ration of an emulsion of water-repellent material, in which the average particle size of the majority of individual particles of the water-repellent material is preferably of the order of 5 microns (0.005 mm), with a minimum of 3 microns and preferablya maximum of 10 microns. A further object is the provision ofprimary emulsions having a dispersed phase of solid or semi-solid water-repellent substances that upon dilution will transform into secondary emulsions comprising a voluminous fiocculent aqueous mass '10 which generally have 40% and more finely disof minuteiiocks 01 particles or the water-repellent substance which are free from any tendency to agglomerate and that may subsequently be diluted and mixed to any extent without destroying the flock characteristic.

Another object of. the invention is to form an aqueous emulsion of high melting point waterrepcllent materials using a solventasan aid in emulsiiication in such amolmts, however, as not to prevent the formation of a dispersed phase of substantially solid particles following emulsiflcation.

Another object is the provision of a highly efiective integral waterproofing emulsion adapted to markedly improve the water-resistance of cellular products without substantially decreasing the percentage of unfilled voids.

Another object is to form an emulsion in concentrated form suiiiciently stable to permit handling and storage, which does not include any stabilizing or peptizing agents.

It is another object of thepresent invention to provide a method for producing a highly effective integral waterproofing emulsion which is especially adaptable for reducing the moisture absorption of cement and cement-fiber composi lions.

It is a further object of the invention to proyide a novel and improved method of producing paraflin emulsions, particularly for the purpose of waterproofing agents within cement-fiber.

products, and which provides excellent waterproofing results with relatively small-amounts of emulsion, i. e. out of all proportion to the amount of emulsion used. V Still another object is the provision of a highly efiective integral waterproofing emulsion for products made of a finely divided aggregate and a binder.

Another objectis the provision of an emulsion oi the oil-in-water type having a pH value of Y about I toabout 8.5, which upon dilution with tion o1 an emulsion of relatively unstable char- "aotersufiicientlystabletobehandledandstored without breaking down and that transforms into a secondary emulsion upon dilution, having altered but stable A specific object of my invention is to provide an emulsion of the oil-in-wflter p in which the dispersed phase consists of small individually mobile groups of solid or semi-solid particles of the ca constituting said phase. which groups exhibit adherent tendencies when brought into contact with materials to be made moistrn'e resistant and which are not readily lostin fil- Another object is the provision of a concentrated ernulsion-i'orrnedby dilu in a primary emulsion having a dispersed phase comprising solid orsemi-solid particla' to cause ironstormafionto the secondary form andsubsequmflyremovingflreexcess portion of the con- An additional object is the provision. of an unstable aqueousemulsionthattransiorms upon dilution at apH of about 6.8 (tap water). into a emulsion having difl'erent characterlt'iis also within the contemplation of the invention to provide an unmable paraflin emulsion of novel character which can be advantageously Other and further objects and advantages of I the invention will become apparent from the following description taken in conjunction; with 15 the following illustrative examples. Broadly stated, according to my invention, I provide principles which are a complete departure from the conventional principles employed in prior water-proofing emulsions. Prior emulsions were generally of the oil-in-water type; invariably' included stabilizing and peptizing agents; had the greatest possible stability at all dilutions and had the smallest obtainable particle size, usually about rt,- of a micron and hardly ever over 2 microns. The reason that oil-inwater emulsions were used was their ready miscibility with water in all proportions, whereas this is not the case with .water-in-oil' emulsions. Moreover, it was expected that by having good stability and small particle size, the emulsion would not be subject to breaking down in the orfiltered in forming matrices thereof, there is con- :siderable loss of the water-repellant agent 'during the filtering and dewatering operations due to the fineness of the Particles and due to-the facility with which the particles are carried away by the water. Also, a prior oil-in-water emulsion does not readily adhere to a. surface with which it comes in contact as compared to a water-in-oil emulsion, the adherence of which is generally very good. Moreover, the quantity of the water-proofing agent which is actually retained and is distributed in the voids of the finished product is very ineffective, probably because of the smallness of the mobile emulsion particle in comparison to the size of the voids. The size of the voids in certain products is often about 50 to 150 microns, whereas the average size of the conventional emulsion particles is generally not over 2 microns and more usually -of a micron. This situation is further aggravated by the fact that the mobile particle of the prior oil-in-water emulsion oiiers no resistance to the how of water arormd it. In other words, in emulsification it'has lost its waterrepellent property as an individual particle. The particle may be washed about readily in dilution, or if held in place in the finished product, it will not resist the flow of water by its surface. Thus, the water will readily force its way into the voids of the finished product by capillary action in spite oi the presence of such particles in and on the walls of'the-voids. V

Accordingly, it is the basic concept ofmy inventionto provide a primary emul- 'sion comprising a dispersed phase of mobileindividual solid or semi-solid, i. 'e.

solid, particles having substantially nonadherent aaeae'n which dispersed phase is transformable without reversion upon dilution into a secondary emul sion of mobile individual groups of associated individual particles which retain their water-repellent properties and which grouped particles exhibit a tendency of strongly adhering to surfaces with which they come in contact. Also I provide, where desired, a concentrated secondary emulsion of-this type by removal of the excess water from the dilute emulsion as form'ed. I have found that to satisfy these considerations, the preferred emulsion is preferably a readily transformable one adapted to handling and storage without breaking and contains a. major portion of particles of large average size in excess ofone micron, preferably about and under microns,

and although normally comprising mobile individual particles of the dispersed phase of an oiliii-water type emulsion inconcentrated form, to be of such character as to be transformed into what is believed to be a similar type emulsion differing in that it is completely stable under all dilutions and consists of mobile individual groups of associated-individual particles. Preferably, the

emulsion comprises a dispersed phase of water-repellent material having arelatively high melting point so that it willbe in solid'or semi-solid state at the temperatures at which it is employed.

Theemulsion has to be of such a stability that it will transform .by mere dilution to the final cbndition in which it may be used in making the composition in question .to be waterproofed and will not require breaking with or without the use of strong electrolytes, which is necessary to precipitate the dispersed phase of a stableemulsion as typified by rtheprior art. With the trans formed emulsions of my invention, adherence is an inherent property of'the dispersed phase and no precipitation is necessary. The transformation from the primary to the secondary condition is gradual and not sharp. Also, the primary emulsions .of my invention provide at the trans'-.

formation point-particles of flocculent character which form into individual groups of small numbers of contacting particles and which remainso I constituted, irrespective of further dilution. In

general, eachgroup comprises-about 10 or'more particles. The number will depend upon the wate'r-repellent substance and the size of the individual particles forming the emulsion.

I do not know exactly the cause of the transformation from the primary-to the secondary emulsion but I believe that the initially weak films of dispersing agent surrounding the individual particles of [the dispersed phase are further weakened by dilution. This may cause the particles to be influenced by electrical charges believed to be set up in the initial emulsification.

advantages and from the angle of its processing,

use and effectiveness inwater-prooflng, it isjhe preferred substance.--I araflin' has a relatively high melting point. Paraflln also has a low doe greeof adhesion and I have foundthat it forms readilytransformable primary, emulsions of the invention in dilute soap-solutions having a pH value near the neutral point and under proper conditions can be processed to the proper degree of stability. When diluted, the paraflin primary emulsions of the present invention transform gradually under proper conditions into the secondary emulsions of the invention. .Moreover, paraifin can .be readily, processed inaccordance with the principles of the present invention without the use of any additional chemical agents, is very economical to use, and has excellent waterrepellent properties.

To obtain the preferred dispersion of parafiin, I prefer to use a commercial dispersing agent. I have found that a small amount, less than about 10% of the weight of the paraffin, of soluble soap stock of the sodium or potassium fatty acid type, for instance, rosin laundry soap stock or commercialliquid potassium stearate soaps, or the like, are effective. I prefer to use a 2% aqueous solution. Other dispersing agents such as linolea-tes or caseinateawhile not as desirable by reason of cost, etc., may be employed. Moreover, the dispersing agents may be combined. I employ the paraffin in the liquid, preferably molten state, and either pour it into the hot or substantially boiling soap solution, or prefera b'ly heat the paraflintogether with (the soap solution until the parafiin has completely melted. Obviously, if desired, the soap might be added at any other step during the preparation of .the liquid paraffin. ,This is not as satisfactory as the foregoing methods. L V

The pH of the parafiin solution should preferably be in the proximity of 7 to 8.5, but not under 6.5. I have found that under such conditions, it is rather difficult .to emulsify the parafiin and that ordinarily it would not be expected to obtain substantially complete emulsification. However, if the degree of agitation under which the emulsion is produced, is controlled with proper accuracy, the difficulty is overcome. Thus, if the agitation is not vigorous enough, and the parafiin is not subjected tosufllcient shearing action, no complete emulsification will be obtained and more or less of the paraffin will collect in comparatively large particles or even inlumps at the surface of the mixture. on the other hand,if the agitation is too vigorous, the emulsified paraflin tends to coalesce during the process and forms similar lumps collecting at the surface. Also, under certain conditions, as when a considerable amount of air is drawn into the body of the mixture, a very fine particle size is obtained, which, of course, is not preferred for the purposes of the present invention. 7 I

I have found that a 5 gallon mixer having a flat propeller blade set almost straight, or preferably a circular blade with a corrugated facing and also set almost straight, produces considerable shearing action at about 3,500 R; P. M. with a of agitation in the body of the liquid, and provides proper particle sizes and very satisfactory results. After complete emulsification has taken place, the time required is dependent upon the volume of material being operated upon, the is interrupted and the emulsion is allowed to cool. When cold, the concentrated part of the. parafiln emulsion usually settles toward the top in a foamy cream layer and comprises individual particles in the solid or semi-solid state. For

--' this reason the mixture is thenslowly stirred mass of material to be waterproofed.

Generally, the average particle -size will de termine the amount of dispersing agent essential for the primary emulsion. In the preferred range (-25 microns), about a 2% solution will be found satisfactory in most cases. If the average particle size of the majority of particles is less than 1 micron more in the order .of

microns, I have found that a primary emulsion may be made only if a very small amount of dispersing agent, for instance, solution, is

used. However, a primary emulsion of this character, in order to be transformed into the secondary emulsion type, must be diluted to a point where any waterproofing results therefrom would be far less than that obtained where the particle size is the preferred one. .On the other hand, if the average particle size of the majority of particles is in the order of 30-50 microns, a greater amount of dispersing agent is required to prepare the primary emulsion. I have discovered that such particles transform into the secondary emulsion at a higher pH value than a primary emulsion of the preferred particle size and have found that in certain cases the amount of dilution is not sufficient for good results. Even if it were, a non-uniform particle size is existent as it is almost impossible to obtain large particles without the presence of a great deal of small particles and such invariably causes excessively large flocks to be formed that are detrimental to the distribution in a Also, an excess of soap dispersing agent should be generally avoided as it may affect the waterproofing properties of the emulsion and may be detrimental with certain compositions to which the emulsion is added. Accordingly, where best waterproofing results are desired, the preferredparticle sizes should be obtained.

.For the purpose of giving those skilled in the art a better understandingof the invention, the

following illustrative example is given.

Example No. 1

About 0.2 pounds of commercial sodium stearate soap is dissolved in about pounds of water. 10 pounds of ordinaryparaflin wax having a melting point of 128 F. is added to the solution, which is heated until all of the wax is melted. The mixture is now subjected to the action of a high speed mixer of the type described hereinabove until it is completely emulsifled to a foamy cream. This will require about 3 to 4 minutes. Thereafter, the mixture is allowed to stand for several hours in order to cool.

stored without deterioration for any length 'of time. The emulsion may be diluted to a con siderable 'degree before showing any=signs of transforming into the secondary emulsion. m

'nated naphthalene),- shellac, or beeswax, are exaasaar'r use, it may be mixed with a dilute composition to be waterproofedin concentrated form or may first be diluted to the "secondary" condition, and then added. If dilutedbelow about 5% parafin content, the primary emulsion will transform into the secondary emulsion. The flocks found are small, about 5" inch in diameter, and a microscopical examination will show them to be small aggregates of individual particles of the paraffin, each still having the same size as the individual particles of the-dispersed paraflin in the primary emulsion, that is, about 5 to 25 microns. when allowed to collect at the surface, the plurality of flocks is readily broken up and the individual flocks are dis-. persed throughout the water by a slight shaking. In contrast to the individual dispersed paraffin particles of the primary emulsion, these flocks adhere to surfaces with which they come in contact and. are capable of sticking even to glassy surfaces. This phenomenon is much similar to the well known behavior of water-in-oil emulsions, and since these small groups of particles engulf and carry with them minute particles of water, individually they may be considered as a water-in-oil emulsion member of an oil-in water emulsion. It is of great importance that the primary emulsion prepared in accordance with the present invention will form small flocks when highly diluted, andthat these flocks will not agglomerate into large masses.

It will be noted that as a result of the above characteristics, the primary emulsion embodying the features of my invention is convenient to handle, can easily be diluted to the point at which the fiocculent parafiin is formed, and in this' pellent solids or semi-solids having a melting' point above the atmospheric temperature at which they are used, as waxes, ester gums, and/or natural and synthetic resin materials, of which Chii nese wax,'carnauba wax, rosin,-'Halowax (chlori-' amples, may be used in the place of paraflin with substantial waterproofing results. Bituminous high melting point, may also be employed. Solvents for example, turpentine, toluol, benzine,

materials, such as asphalt, having a sufliciently alcohol, petroleum or ofl, may be used where it is I desired or essential to obtain lower viscosities andlor melting points. However, these solvents should .be'used in amounts as small as posible so that at least the major portion thereof will be evaporated or otherwise removed from the mixture prior to transforming the-primary emulsion into the secondary emulsion, itbeingessential that the particles of the primary emulsion be in asolid or semi-solid state at that time. Where high temperature materials are used, the processing may also be conducted under pressure conditions to avoid excessive ebullition.

In all cases, it is preferred 'to use a relatively weak dispersing agent, such as a soap solution,

generally having a concentration of about 2%.

15 some idea as to the procedure to be employed with substances other than paraflin.

- Example N0. 2

About 10 lbs.- of ordinary commercial rosin hav- 20 inga melting point of about 110 C. are melted and about 0.5 lbs. of turpentine are added. This addition has the object of lowering the viscosity and the melting point in order to avoid pressure operations. About 0.6 lbs. of a potassium stearate 25 soap are then dissolved in about 10 lbs. of boiling water. The melted rosin is then gradually run into the soap soluti'on while the mixture is being subjected to the action of a highspeed mixer, as

' described in Example No. 1. 3 tendency in this type of mixture to form a waterin-oil emulsion, when the concentration of soap is too low because of the moderate emulsifying shearing action that is being employed. For this reason, as will be noted, a considerable amount of.

35 soap is used. The proper mixture will be recognized by a considerable tendency to foam and the finished primary emulsion will be a very foanrv product.

The finished primary emulsion in this case is very foamy but there is a greater variation in the particle size than in that of Example No. 1; that is this emulsion will generally contain a number of particles considerably above the average size. This is probably due to the difficulty with which a the material is sheared apart, and in trying to obtain a particle of preferred size, some oversized particles seem to be unavoidable. However, this emulsion acts similar to the paraflin in that it transforms into the secondary emulsion upon 50 dilution or upon mixing with the dilute composition, which it is intended to waterproof. The secondary emulsion of this material has greater adhering tendency than the secondary paramn emulsion and therefore has a slight tendency to congeal into small masses when brought together.

For this reason, it is preferred to mix this primary.

emulsion right in with the composition to bewaterproofed while diluting, when it is being used.

Example No. 3

About 10 lbs. of chlorinated naphthalene sold under the trade-mark Halowax? having a melting point of about 170 F. are melted and poured into' 10 lbsrof hot soap solution containing about- 0.8 lbs. of sodium stearate. v The mixture is subjected toan emulsifying action as described in v Example No. 1;] The finished emulsion in this case is very similar to'the paraffin emulsionof Example No. 1, but there is inthis'case a tend- 7 ency toform a considerablenumber of small particles just as therewas a tendency to formsome large particles with vthe rosin of Example No.2-

The variation fr'omji e average is generally not so great er aswith the rosin. The general u a 'l w s ts li ere'aa in a lhe There is a' strong use of any clays or alkaline additions. Furthernecessarily requires a 'water repellent agent cases. This primary Halowax" emulsion starts to transform into the secondary emulsion when dilutedto below about 15% Halowax" content.

In this case the secondary emulsion" particles also have a greater adhering tendency than is the case with the-secondary parafiinemulsion of Example No. 1. 'I have found the'secondary emulsion of Halowax to be quite eflective but not as good as the paraflin for reducing moisture absorption in a composition with which it is in- 10 tegrally mixed.

' Example No. 4

About 10 lbs. of Chinese wax are substituted forthe Halowax in Example No.'3 and the emulsion is prepared in the same way. The finished product will be found to be very similar to the primary parafiin emulsion of Example No. 1. .In this case, the secondary emulsion will adhere to surfaces as will the paraflin, but there is not as much sticking tendency as with the rosin or the Halowax of Examples Nos. 2 and 3, respectively.

Example No. 5

About 5 lbs. of Egyptian asphalt and 5 lbs. of paraflin are melted together and this mixture is substituted for the paraflin in Example No. 1. The primary emulsion is prepared in the same way. The finished primary product is similar to the primary paraffin emulsion of Example No.

'1 in stability and general behavior on dilution.

It is not as eifective in the secondary state for reducing moisture-absorption as is the secondary emulsion in which paraflin is used alone.

It'is to be noted that the process of the present invention provides important advantages. Thus, it avoids the conventional practice of employing bentonite and various types of clays in the preparation of bituminous and wax emulsions. -These'agents produce very stable emulsions. It has also been common practice, particularly in the preparation of rosin and resin emulsions, to add additional alkaline reagents to further facilitate the emulsification. This also is 45 avoided by the presentprocess wherein a primary'emulsion is formed with a' pH value near the neutral point, and which has suflicient stability to be handled or stored, yet without the more, it is necessary to add an acidic agent, usually alum, to precipitate the rosin. In contrast to this, in using the primary emulsion of the present invention, no precipitating agents of any kind are needed. Furthermore, the present invention avoids the use of peptizing a ents,

,such as casein or glue, etc., which are frequently used to facilitate and to stabilize the dispersion. Of course, dispensing with all such additional substances renders my process more economical than any of theconventional processes.

"It' is also to be observed thatwhile conven tionalintegral waterproofing emulsions very often employ water-repellent agents of low melting point, therprocess ofthe present invention having amelting point whichis high eno F have the agent in the solid or semi-solid phase at the working atmospheric temperature}: .U. 8. Patent No. 1,913,431; specifies. theiuse of "a. lubricating oil whichwould be liquid atthe Wdrking atmospheric Likewise, bitufm of law- .m t ne' mm re: er l men y employed. Such emulsions do not transform as the primary emulsions of my invention and when broken, precipitate particles which agglomerate into compact masses.

Finally, whereas the conventional emulsifying processes generally employ emulsifying devices of high dispersing power, such as colloid mills, the process of the invention calls for a type of dispersing action which disperses the waterrepellent material in comparatively large particles of about 5 to 25 microns and eliminates the use of colloid mills which would produce a particle size well below 1 micron.

Of course, those skilled in the art will readily understand that the process of the invention is much more critical in the control of the various factors than any of the conventional processes. It is generally quite easy to produce conventional highly stabilized emulsions 'of very small particle size by using high powered dispersing apparatus, such as colloid mills and stabilizing additions. In contrast to this, it will be readily appreciated that the process of the present invention which involves obtaining a critically adjusted degree of stability will be very sensitive to changes in pH, in temperature, and the results will be greatly influenced by the type of dispersing agent, tap water and dispersing action employed. However, all of these variables can be easily determined and a completely satisfactory primary emulsion of proper stability and large particle size, or secondary emulsions stable at all dilutions, can be readily obtained in accordance with the principles explained in the foregoing.

It is also to be noted that the present invention provides primary and secondary emulsions having novel characteristics which will readily appear when examining the emulsions of the invention under the microscope. Thus, the primary paraflin emulsion of the invention shows countless individually suspended mobile particles having sizes varying from about 2 to about .25 microns. The secondary parafiin emulsion em.- bodying the invention shows small groups of associated or aggregated particles. The individual particles usually may be distinguished within the groups.

The primary rosin emulsion of the invention shows individually dispersed particles similar to those of the primary paraflin emulsion but there appears to be a greater variation in the size of the individual particles, the major portion of the particlw being of the larger sizes. The secondary rosin emulsion shows groups of associated or aggregated particles with a tendency of forming somewhat larger-sized groups. The groups appear to have more of an agglomerated characteristic.

The primary Halowax emulsion shows individually dispersed particles, the average size of which is somewhat smaller than those of the primary paraffin emulsion, and fewer large a1 particles mate ng an ant groiips oin associate tl'ierliibfilais'tic waterrpeirent stai tiany-soiiai'statepthesaiii pmitie groupsexiouibitrug'rgeod qnnerentsdiiauties witit respt to 'eentactifi materials fihdtne lfidfvidfial -parti eies '15 eziesiii Elam isiirnia ,ioyewori .eeiialeeios'rsac .r

emulsion of a thermoplastic water-repellent substance having in the continuous phase an aqueous body of soluble soap of less than 12 /2 percent concentration and having in the dispersed phase individual mobile particles of said water-repellent substance having sizes of about 2 to about 25 microns with an average particle size of the majority in the order of 5 microns and in amount such that for every 10 parts by weight of waterrepellent substance there is at least 8 parts by weight of combined water and soap; the said emulsion having a creamy character before and after' solidification of the dispersed phase and having sutficient stability for handling and storage without aid of stabilizing agents and its water-repellent particles having substantially non-adherent properties, and said emulsion adapted upon dilution with water in the absence of electrolyte to form an emulsion of similar type in which said particles of water-repellent substance are associated into mobile groups having good adherent properties.

2. A waterproofing composition comprising an emulsion of a thermoplastic water-repellent wax having in the continuous phase an aqueous body of soluble soap of less than 12 percent concentration and having in the dispersed phase individual mobile particles of said wax the average particle size of the majority of which is in the order of 5 microns with a minimum of 3 microns and a maximum of about 10 microns and which are in amount such that for every 10 parts by weight of wax there is at least 8 parts by weight of combined water and soap; the said emulsion having a creamy character before and after solidification of the dispersed phase and having sufiicient stability for handling and storage without aid of stabilizing agents and its water-repellent wax particles having substantially non-adherent qualitim; and said emulsion being adapted upon substantial dilution with water in the absence of electrolyte to form an emulsion of similar type in which said particles of water-repellent wax are associated into mobile groups having good adherent properties.

3. A waterproofing composition comprising an emulsion of paraffin wax having in the continuous phase an aqueous body of soluble soap of less than 2 percent concentration and having in the dispersed phase individual mobile particles of said paraffin wax the average size of the majority of which is in the order of about 5 microns and in amount such that for every 10 parts by weight of paraflin wax there is at least 8 parts by weight of combined water and soap; the said emulsion having a creamy character and having suflicient stability for handling and storage without aid of stabilizing agents and its particles having substantially non-adherent properties and said emulsion being adapted upon dilution with water in the absence of electrolyte ncentration to forr n a dispersed -p t prising athe ts-atria pa" a);

, cassava a I '7' of said groupshaving sizes of about 2 to about 25 microns with an average particle 'size of .the majority in the order of 5 microns; said emulsion being sufficiently stable for handling and applica- 5 tion without aid of stabilizing agents and being water and a dispersing agent soluble in a solvent comprising water, and a dispersed phase compris- 5' ing particles of a thermoplastic water-repellent 1 war: in .a substantially solid state the average particle size of the majority of which is in the order of about-5 microns, said dispersing agent being present in amount less than 10 percent. by

weight of thewater-repellent wax and said water' and'dispersing agent combined being present inan amount between 80 percent to about 150 percent by .weight of said water-repellent wax; said emulsion having a creamy character and having suflicient stability forhandling and storage without. aid of stabilizing agents and the water'- repellent wax particles thereof having substantially poor adherentproperties and said emulsion being adapted .upon' dilution. with water in the 3o"absence of electrolyte to form an emulsion in which said particles of water-repellentwax are associated into mobile groups exhibiting good adherent properties. n

6. A waterproofing composition comprising an 33- emulsion having in the" continuous phase an aqueous body of a water-soluble fatty acid soap of' a univalent metal and having'in the dispersed phase individual; mobile particles of a thermoplastic water-repellent substance having amelt- 4g ing point substantiallyabove 70"F., said water and dispersing agent being present in a quantity of at least about IO percent and less than about 10- percent by weight respectively of the waterrepellent substance and said water-repellent sub- 45 stance. being present.in particles average size between 5 to- 25 microns, said emulsion being characterized by its ability-to transform. upon substantial dilution forming a voluminous flocculent mass consistingof small d0 individual mobile flocks of said particles, sub-, stantially freefrom tendency to agglomerate into a solid mass.

' 7'; A waterproofing composition comprising an emulsion including 1 part paraflin'wax, about 1 U5 part water, andabout ,6 part and less of sodium stearate soap; said waterandsoap formin a continuous phase and said paraflln wax consisting of v individualmobile particles thereof the average size of the majority of which is in .the order of 60 5 microns with a minimum of 3'microns and a maximum: of about 10 microns, and forming the dispersed phase, and the said paraffin particles exhibiting non-adherent qualities; said emulsion havinga creamy character and having sufficient I V 65 stability "for handling and storage without aid i 'of stabilizing agents and said emulsionadapted upon aqueous dilution in the absence of electrolyte-toabout. 5 percent concentration to form "an emulsion of. similar typein-whichsaid in;- 70 dividual particlesof associated. intomobile groups' havinggood adherent proper ties.

8. ,li'he method of preparing an emulsio of the- 7 n -for handling andlstorage without the aid of;

istabilizingagents. and being capable of trans- I6 type having a continuous phase containing a "large amount of water and afsmall amount of dispersing agent, which comprises forming a liquid mixture comprising a large amount of 1 water, a thermoplastic water-repellent substance substantially solid at normal atmospheric temperatures, and a small amount of a water soluble. 5 soap dispersing agent, said dispersing agent dissolving in said water to produce a dilute solution and having a concentration in said water ofless than 12 /2% by weight, and said combined water and dispersing agent being present in an amount 10 at least 80% by weight of said water-repellent substance; dispersingssaid water-repellent substance with high speed mixing in said dilute solution of dispersing agent, and during said mixing reducing said water-repellent substance to 15 particles having sizes of about 2 to about microns with an average particle size of the majority in the order of 5 microns, and forming an emulsion of. creamy character having said water and dispersing agent in the continuous 2 phase and said particles of water-repellent substance in the dispersed phase, and having said combined water and dispersing. agent present in 1 anamount at least 80% by weight of said waterrepellent substance; the said emulsion retaining 25 its creamy character before and after solidification of said thermoplastic water-repellent substance, the particles of water-repellent substance thereof exhibiting substantially. non-adherent properties and said emulsion possessing suflicient 3o stability for handling and storage without the aid of stabilizing agents, and being capable of transformation upon dilution with water in the absence of electrolyte into a secondary emulsion. having the dispersed phasepresent as individual groups of associated individual particles which I possess water-repellent properties and which grouped particles exhibit -a tendency of strongly adhering tosurfaces with which they come in contactlto waterproof the'same;

-9. The method of preparing an emulsion of the type having a continuous phase containing a large. amou'ntof "water. and asmall amount of dispersing agent, which comprises forming a liquid mixture comprising. a large amount of water, a water-repellent wax substantially solid at normal atmospheric temperatures, and a small amount of a water soluble soap dispersing agent,

j said dispersing agent dissolving in said water to produce a dilute solution. and having a concentration. in said water of less than 12 %'by weight, and said combined-,waterand dispersing agent being present in an amount at least 80% by I weight of said water-repellent substance; dispersing said water-repellent substance with high speed mixing in said dilute solution of dispersing agent, and during said mixing reducing said water-repellent substance to particles the average size of the majority of which is in the order of 5':

microns with a. minimum of 3 microns and" a maximu'ni'o'f about 10 microns, and forming an emulsion of creamyv character having said water and dispersing agent in the continuous phase and character before and after. 'solidificationfof said thermoplastic water-repellent substance, the 7 particles of water-repellentsubstance thereof exhibiting substantially non-adherent properties,

and'saidemulsion possessing suiilcient stability 6 possess water-repellent properties and which grouped particles exhibit a tendency of strongly adhering to surfaces with which they come in contact to waterproof the same.

10. The method of preparing an emulsion of the type having a continuous phase containing a large amount of water and a small amount of dispersing agent, which comprises forming a liquid mixture comprising a large amount of 15 water, a paraflin wax, and a small amount of a persing agent dissolving in'said water to produce a dilute solution and having a concentration in said water of less than 2% by weight, and said combined water and dispersing agent being present in an amount at least 80% by weight of said parafiin wax; dispersing said paraflin wax with high speed mixing in said dilutesolution of dispersing agent, and during said mixing reducing said paraflin wax to particles the average size of the majority of which is in theorder of about 5 microns, and forming an emulsion of with water to about 5% paraflin content, in the absence of electrolyte, into a secondary emulsion having the dispersed phase present as individual groups of associated individual particles which possess water-repellent properties and which grouped particles exhibit a tendency of strongly adhering to surfaces withwhichthey come in contact to waterproof the same.

11. The method of preparing an emulsion of the type having acontinuous phase containing a large amountof water and a small amount of dispersing agent, which comprises forming a liquidunixture comprising alarge amount of water, a thermoplastic water-repellent substance substantially solid at. normal atmospheric tempera'.-. tures, and a' small 'amount of a watersoluble soap dispersing agent, said dispersing agent dissolving in said water to produce a dilute solution Y and having a concentration'insaid water of less than 12/;% by weight, and said combinedwaob ter 'and dispersing agent being present in an amount at least 80% by weight of saidwaterrepellent substance; dispersing said water-repellant substance with high speed mixing in said Y dilute solution of dispersing agent, and during said mixing reducing said water-repellant substance to small wparticleshavingan average size between 5 to about 25 microns, and forming an emulsion of creamy character having said water and dispersing agent in the continuous phase and sai particles of water-repellant substance in the ersed phase, and having saidcombined water and dispersing agent present in an amount at least 80% by weight of said water-repellant substance; the said emulsion retaining its creamy 1 character before and after solidification of said water .soluble soap dispersing agent, said disbeing capable of transformation upon dilution I the type having a continuous phase containing a thermoplastic water-repellent substance, the

particles. of water-repellant' substance thereof exhibiting substantially non-adherent properties, and said emulsion possessing suflicient stability for handling and storage without the aid of 8 stabilizing agents; and subsequently diluting the aforesaid emulsion with water in the absence of electrolyte to form a secondary emulsion having the dispersed phase present as individual groups of associated individual particles which possess 10' I water-repellant properties and which grouped particles exhibit a tendency of strongly adhering to surfaces with which they come in contact to waterproof the same.

12. The method of preparing an emulsion of the type having a continuous phase containing a large amount of water and a small amount of dispersing agent, which-comprises forming a hot liquid mixture comprising alarge amount of we.- ter, a melted thermoplastic water-:repellant substance substantially solid at normal atmospheric temperatures, and a small amolmt of a water soluble soap dispersing agent, said agent dissolving in said water to produce a dilute solution and having a concentration in said wai ter of less than 12%% by weight, and said combined water and dispersing agent being present in an amount of about 80% to 150% by weight of said water-repellent substance; dispersing said water-repellent substance wi h h speed 80 mixing in said dilute solution of dispersing agent, and during said mixing reducing saidwater-repellant substance by an action characterized by a narrow flat propeller blade set almost straight and operated at about 3500 R. P. M. toparticles having an average size between about 5 to 25 microns, and forming an emulsion of uniform creamy having said water and dispersing agent in the continuous phase and said particles :of water-repellant substance in the dis- '40 persed phase, and having said combined water and dispersing agent present in an amolmt at least 80% by weight of said water-repellent substance; the said emulsion retaining its creamy character before and after-solidification of said thermoplastic water-repellent substance, the

,particles of water-repellantsubstance thereof exhibiting substantially non-adherent. properties, and said emulsion suificient stability 7 for handling and storage without the aid of B0 stabilizing agents. and being capable of transformation upon dilution with water in the ab sence of electrolyteinto a secondary emulsion having the dispersed phase present as individual groups of associated-individual particles which 68 possess water-repellant properties and which grouped particles exhibits tendency of strongly adhering to surfaces with which they come in contact to waterproof the same.

13. The method of preparing an emulsion of large amount of water and a small amolmt of dispersing agent, which comprises forming a liquid mixture comprising a large amount of water, a thermoplastic water-repellant substance 'substantially solid at normal atmospheric temperatures, and a small amount of a water soluble soap dispersing agent; said dispersing agent dissolving in said water to produce a dilute solution and having a concentration in said water of less than 12% by weight, and said combined wateranddispersing'agentbeingpresent inan" amount at least by weight of said water repellant'substance, and emulsifiing the aforesaid liquidmixture with hleh'speed mixing and."

assaorv with shearing oi said waten-repellant substance to particles of a size intermediary between colloidal size and large emuis size and ranging in majority between about a about 25 rzzicrons. and forming an emulsion hi t'lllg a cr amy character and having said water and dispers ng agent grouped particles exhibit a tendency of strongly adhering to surfaces with which they come in contact to waterproof the same.

14. The method of preparing an emulsion of the type having a continuous phase containing a large amount of water and a small amount of dispersing agent,-which comprises dissolving a small amount of a water soluble soap dispersing agent in a large amount of water to form a dilute aqueous soap solution having a concentration of said dispersing agent in said water of less than 12 /2% by weight, introducing into said dilute aqueous soap solution molten liquid thermoplastic waterrepellent substance while said solution is in a heated condition, said combined water and dispersing agent being present in an amount at least 80% by weight of said water-repellent substance. subjecting said dilute aqueous soap solution containing said water-repellent substance to high speed mixing to disperse said water-repellent substance in said solution and :0 a mixing: sufficiently vigorous to shear said water-repellent substance into individual mobile particles the majority of which are under 25 microns in size, but insufiicient to convert said particles :0 a majority of a size less than about 5 micron cooling the mass to form an emulsion of the raster of creamy foam having said water and dispersing agent in the continuous phase and said particles of waterrepellent substance in the dispersed phase, and having said combined water and dispersing agent present in an amount at least 80% by weight of said water-repellent substance; and stirring the emulsion to form a uniform cream; the said emulsion retaining its creamy character before and after solidification of said thermoplastic water-repellent substance, the particles of waterrepellent substance thereof exhibiting substantially non-adherent properties, and said emulsion possessing suflicient stability for handling and storage without the aid of stabilizing agents, and being capable of transformation upon dilution with water in the absence of electrolyte into a secondary 'emulsion having the dispersed phase present as individual groups of associated individual particles which possess water-repellent properties and which grouped particles exhibit a tendency of strongly adhering to surfaces with which they come in contact to waterproof the same. i

15. The method of preparing an emulsion of the type having a continuous phase containing a large amount of water and a small amount of dispersing agent, which comprises forming a hot dilute aqueous solutioncontaining a large amount of water and a small amount of a water soluble soap dispersing agent, said dispersing agent having a concentration in said water of less than 12 96 by weight, introducing molten liquid best gymnasts coer watel' repelient was: into said hot dilute aqueous solution, said combined water and dispersing agent being present in said solution in an amount at least 80% by weight of said water-repelleni wax and s; ibjecting said dilute aqueous soap solu tion coniaiiiing saidmolten liquid wax to high speed agitation to disperse said wax in said ep solution and to a shearing action sufficient to re duce the majority of the particles of said wax t6 a size less than about 10 microns but insufiicient to reduce the majority of said particles to a size less than about 3 microns, whereby complete emulsification' is obtained without obtaining athe absence of electrolyte to produce a secondary emulsion having the dispersed phase present as individual groups of associated individual particles which possess water-repellent properties and which grouped particles exhibit a tendency as" strongly adhering to surfaces with which they come in contact to waterproof the same,

16. The method of preparing an emulsion of the-type. having a continuous phase con aining a 'large amount of water and a small amount oi dispersing agent, which comprises forming a liq 1i uid mixture comprising a large amount of wat r a thermoplastic water-repellent substance sub stantially solid at normal atmospheric temperatures, and a small amount of water soluble soap dispersing agent, said dispersing agent dissolvin in said water to produce a dilute solution and having a concentration in said water of less than 12 /2% by weight; and said combined water and dispersing agent being present in an amount at least 80% by weight of said watenrepellent substance; dispersing said water-repellent substance in said dilute solution of dispersing agent by a high speed agitation sufiiciently vigorous to reduce said water-repellent substance to small particles having an average size between about 5 to about 25 microns, thereby forming an emulsion of creamy character having said water and dispersing agent in the continuous phase and said particles of water-repellent substance in the dispersed phase, and having said combined water and dispersing agent present in an amount at least 80% by weight of said water-repellent substance; the said emulsion retaining its creamy character before and after solidification of said thermoplastic water-repellent substance, the particles of water-repellent substance thereof exhibiting substantially non-inherent properties and said emulsion possessing suflicient stability for handling and storage without the aid of stabilizing agents, and. being capable of transformation upon dilution with water in the absence of electrolyte into a secondary emulsion having the dispersed phase present as individual groups of associated individual particles which possess water-repellent properties and which grouped particles exhibit a tendency of strongly adhering to surfaces with which they come in contact to 

